CN1296467C - Low-friction sliding member in transmission, and transmission oil therefor - Google Patents

Low-friction sliding member in transmission, and transmission oil therefor Download PDF

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Publication number
CN1296467C
CN1296467C CNB2004100641577A CN200410064157A CN1296467C CN 1296467 C CN1296467 C CN 1296467C CN B2004100641577 A CNB2004100641577 A CN B2004100641577A CN 200410064157 A CN200410064157 A CN 200410064157A CN 1296467 C CN1296467 C CN 1296467C
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China
Prior art keywords
acid
sliding part
low friction
thin film
friction sliding
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Expired - Fee Related
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CNB2004100641577A
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Chinese (zh)
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CN1597888A (en
Inventor
石川贵朗
中村清隆
加纳真
上野贵文
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Nissan Motor Co Ltd
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Nissan Motor Co Ltd
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Priority claimed from JP2004230039A external-priority patent/JP4973973B2/en
Priority claimed from JP2004230038A external-priority patent/JP4973972B2/en
Application filed by Nissan Motor Co Ltd filed Critical Nissan Motor Co Ltd
Publication of CN1597888A publication Critical patent/CN1597888A/en
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Publication of CN1296467C publication Critical patent/CN1296467C/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
    • F16C33/00—Parts of bearings; Special methods for making bearings or parts thereof
    • F16C33/02—Parts of sliding-contact bearings
    • F16C33/04—Brasses; Bushes; Linings
    • F16C33/16—Sliding surface consisting mainly of graphite
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16H—GEARING
    • F16H57/00—General details of gearing
    • F16H57/04—Features relating to lubrication or cooling or heating
    • F16H57/041—Coatings or solid lubricants, e.g. antiseize layers or pastes
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    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

A low-friction sliding member in a transmission is at least one of sliding members which are in slidable contact with each other in presence of a transmission oil composition. The low-friction sliding member includes a base material having a sliding section. A hard carbon thin film is coated at a sliding surface of the sliding section of the base material. The hard carbon thin film contains hydrogen in an amount not more than 20 atomic %. The transmission oil composition contains at least one of organic oxygen-containing compound and aliphatic amine compound.

Description

Low friction sliding part in speed changer and the transmission oil for the sliding part
Cross-reference to related applications
The application has following related application: U.S. Patent Application Serial Number 09/545,181, it puts down -11-102205 based on Japanese patent application filed on April 9th, 1999；10/468,713, it is designated state (U.S.) application number of the PCT application JP02/10057 based on Japanese patent application 2001-117680 filed on April 17th, 2001；10/355,099, it was based on 2 months 2002 Japanese patent application 2002-45576 filed in 22 days；10/682,559, it is based on Japanese patent application 2002-302205 filed on October 16th, 2002；And 10/692,853, it is based on Japanese patent application 2002-322322 filed on October 16th, 2002.
Background of invention
The present invention relates to the improvement of the low friction sliding part in speed changer, and relate more specifically to suitable for the low friction sliding part in continuously variable transmission and in automatic transmission, and the transmission oil composition for the low friction sliding part.
The Global Environmental Problems of such as global warming and depletion of the ozone layer just become prominent.Since it is said that global warming is mainly by CO2The influence of discharge, CO2The reduction of discharge, especially CO2The setting of discharge standard has changed into a major issue of various countries' concern.Reduce CO2The challenge of discharge first is that improve fuel efficiency or fuel economy, the performance of the fuel efficiency or fuel economy dependent on sliding part and the transmission oil for the sliding part.It is appreciated that sliding part and transmission oil play main effect in the improvement of fuel economy.
Even if it is required that sliding part in fretting wear environment compared with other sliding positions in speed changer in more serious sliding position, wear resistance is also good.Recently, the application of a variety of hard films is developing.Usually, hard carbon thin film is desired as the low-friction material for sliding part, because hard carbon thin film has low-friction coefficient in air and in the presence of lubricating oil compared with the wear-resistant hard coating material of such as titanium nitride (TiN) or chromium nitride (CrN).
In addition, there is following methods to improve fuel economy related with lubricating oil: (1) lubricating oil viscosity is reduced, to reduce the agitation resistance in the viscous drag and engine in hydrodynamic lubrication area；(2) friction improver appropriate and other additives is added, in lubricating oil to reduce the friction loss under mixed lubrication and condition of boundary lubrication.
These are the 11-12 pages of proceeding, KANO etc. in Japanese tribology meeting 1999.5, Tokyo about the method for frictional behavior related with lubricating oil, and in world's tribology meeting 2001.9, Vienna, discusses in KANO etc. by proceeding page 342.
Summary of the invention
But it also shows, under air with the common hard carbon thin film of excellent low friction characteristic, friction reducing effect in the presence of lubricating oil is not necessarily high, and, even if applying a kind of lubricating oil (composition) containing known organic molybdenum on common hard carbon thin film, such hard carbon thin film can not fully show friction reducing effect.
Therefore, it is an object of the present invention to provide in a kind of speed changer improvement low friction sliding part and a kind of transmission oil composition of the improvement for the sliding part, the problem of thus being encountered in common process can effectively be overcome.
It is a further object to provide the improvement low friction sliding parts in a kind of speed changer, and a kind of transmission oil composition of improvement for the sliding part, pass through the transmission oil composition, sliding part has very superior low friction characteristic, and wear resistance is superior, while steadily showing low friction characteristic in a long time.
One aspect of the present invention is the low friction sliding part in a kind of speed changer, which is at least one of the sliding part being in slidable contact with each other in the presence of transmission oil composition.The low friction sliding part includes the basis material with sliding area.One hard carbon thin film is coated on the sliding surface of basis material sliding area.The hard carbon thin film contains the hydrogen no more than 20 atom %.Here, transmission oil composition contains at least one of organic oxygen-containing compound and aliphatic amine compound.
Another aspect of the present invention is a kind of transmission oil composition for low friction sliding part in speed changer, which is at least one of the sliding part being in slidable contact with each other in the presence of the transmission oil composition.Low friction sliding part includes the basis material with sliding area, and the hard carbon thin film on the sliding surface coated in basis material sliding area.The hard carbon thin film contains the hydrogen no more than 20 atom %.The transmission oil composition contains at least one of organic oxygen-containing compound and aliphatic amine compound.
Summary of drawings
Fig. 1 be as low friction sliding part according to the present invention an embodiment for the gear in continuously variable transmission a tooth partial sectional view；And
Fig. 2 be as low friction sliding part according to the present invention another embodiment for the gear in automatic transmission a tooth partial sectional view.
Detailed description of the invention
The present invention is discussed further below.In the following description, unless otherwise indicated, all percentage (%) is mass percent.
First embodiment
The first embodiment of the low friction sliding part in speed changer according to the present invention is discussed below.
At least one of the sliding part that low friction sliding part in continuously variable transmission (CVT) is in slidable contact with each other in the presence of being fluid (composition) in continuously variable transmission oil or referred to as " CVTF (composition) ".Low friction sliding part includes the basis material formed by such as carburizing SCM420 stainless steel.The SCM material is according to JIS (Japanese Industrial Standards) G 4105.Basis material has a sliding area, is coated with hard carbon thin film on the sliding surface of sliding area.Continuously variable transmission oil (can be described as " lubricating oil ") is used as Ashless friction modifiers containing at least one of organic oxygen-containing compound and aliphatic amine compound.It due to this continuously variable transmission oil, is coated at least one sliding surface of sliding part by hard carbon thin film, therefore sliding part can be to be in slidable contact with each other compared with the low-down friction of routine techniques.The example of low friction sliding part is gear, rotary shaft, parts of bearings etc. in continuously variable transmission.Fig. 1 shows a part of a tooth 10 of the gear for continuously variable transmission.The gear teeth 10 includes basis material 12, which has the sliding surface coated by hard carbon thin film 14.
Hard carbon thin film is formed by such as DLC (diamond-like-carbon) material, which mainly by carbon atom and amorphous is constituted.The DLC material has diamond lattic structure (SP in the bonding mode between carbon atom3Key) and/or graphite-structure (SP2Key).More specifically, hard carbon (DLC) film is by the not hydrogeneous amorphous carbon (α-C) that is made of carbon, hydrogeneous amorphous carbon (α-C:H), or contain what titanium (Ti) or molybdenum (Mo) metallic element were formed as part thereof of metal carbides or metal carbon (MeC).
With the increase of hydrogen content in hard carbon thin film, coefficient of friction increases.Therefore in the present invention it is essential that the upper limit of hydrogen content is 20 atom % in hard carbon thin film.Coefficient of friction when sufficiently to reduce sliding in lubricating oil simultaneously obtains stable sliding properties, and the hydrogen content in hard carbon thin film is preferably more than 10 atom %, more preferably no more than 0.5 atom %.
Hard carbon thin film with so low hydrogen content is obtained by not using the PVD method of hydrogen and/or hydrogen-containing compound substantially, such as sputtering method or ion electroplating method.In this case, it is preferred that in baking reactor and the tool for being used to support basis material, and sufficiently cleaning basis material surface to reduce the hydrogen content in hard carbon thin film, and in film formation operation use not hydrogeneous gas when, carry out the film formation operation of hard carbon thin film.
Hard carbon thin film is formed on the surface of basis material.Since the film thickness of hard carbon thin film is fairly small, surface roughness of the basis material before hard carbon thin film formation greatly affects the surface roughness for the hard carbon thin film being formed on substrate material surface.Therefore, before basis material is not coated by hard carbon thin film, surface roughness (center line average roughness) Ra of basis material is preferably no greater than 0.1 μm.If the Film roughness of basis material is more than 0.1 μm, the convex portion as caused by the surface roughness of hard carbon thin film increases local Hertz ' the s contact pressure to relative component, thus induction of the formation in crack in hard carbon thin film.Surface roughness Ra JIS (Japanese Industrial Standards) B 0601 (: Ra75 is construed in 2001).
Hard carbon thin film preferably has the thickness in measured under 10g load application, range is between 1000~3500 surface hardness or micro-vickers hardness (Hv) and range between 0.3~2.0 μm.If the surface hardness and thickness of hard carbon thin film have exceeded above range, the abrasion that hard carbon thin film will then occur in surface hardness (Hv) less than 1000 and when thickness is less than 0.3 μm, the removing of hard carbon thin film will be prone to when surface hardness (Hv) is more than 3500 and thickness is more than 2.0 μm.
It is particularly effective that low friction sliding part in continuously variable transmission, which is used as the sliding part of continuously variable transmission, the continuously variable transmission has respective slidingsurface, sliding surface sliding contact in the presence of the continuously variable transmission that these surfaces provide between accessible sliding surface is oily, with the relative component formed by iron-based material or aluminium alloy.Continuously variable transmission in the present invention refers to that variable speed operation is the speed changer of continuous mode.One representative instance of the continuously variable transmission has such mechanism: fixed and movable sheave (one coaster of composition) is mounted in each driver and drive shaft, one metal tape is placed among sheave, so that the metal tape transmits on two pulleys being fixed on driver and drive shaft.Therefore, the energy from engine by metal tape from the pulley that the pulley of drive shaft passes to drive shaft, thus continuously carry out vehicle variable speed operation.
Next the continuously variable transmission oil or lubricating oil of continuously variable transmission be will be discussed for.
Continuously variable transmission oil or lubricating oil (composition) preferably include a kind of base oil and at least one of organic oxygen-containing compound and aliphatic amine compound as Ashless friction modifiers.It is noted that very outstanding low friction characteristic will be shown at the slidingsurface of hard carbon thin film coating in the presence of lubricating oil.
Base oil is not particularly limited, it can be any base oil (compound or multiple compounds) commonly used in lubricating oil, such as mineral oil, synthetic oil, any combination of grease (compound) or mineral oil, synthetic oil, grease.
The specific example of mineral oil includes alkenyl group base oil or cycloalkyl group base oil, and normal paraffin hydrocarbons, they are by extracting lube cut from petroleum with normal pressure or vacuum distillation, then the lube cut obtained at least one of following processing purification is to preparation: solvent deasphalting, solvent extraction plus hydrogen decomposition, solvent dewaxing, hydrofinishing, sulfuric acid treatment, clay-filtered etc., these processing appropriate can be used in combination.Gained lubricating oil is usually refined using hydrofinishing or solvent refining.In addition, it is preferable to use the obtained mineral oil of bright stock by using height plus hydrogen decomposition method, the refining methd can greatly reduce aromatic components, and the method mineral oil produced by being used for isomerization GTL (gas to liquid) wax.
The specific example of synthetic oil includes polyalphaolefin (such as 1- octene oligomers, 1- decylene oligomer and ethylene-propylene oligomer), the hydride of polyalphaolefin, isobutylene oligomer, the hydride of isobutylene oligomer, isoparaffin, alkylbenzene, alkylnaphthalene, diester (such as glutaric acid two (tridecyl) ester, dioctyl adipate, diisodecyl adipate (DIDA), adipic acid two (tridecyl) ester, and dioctyl sebacate), polyol ester (such as sad trihydroxymethylpropanyl ester；N-nonanoic acid trihydroxymethylpropanyl ester；Trihydroxymethylpropanyl ester, such as isostearic acid trihydroxymethylpropanyl ester；Pentaerythritol ester, such as caproic acid pentaerythrite -2- ethyl ester, n-nonanoic acid pentaerythritol ester), polyoxyalkylene glycol, dialkyl diphenyl ether and polyphenylene oxide.In these synthesis oil compositions, the preferably polyalphaolefin and its hydride of such as 1- butene low polymers and 1- decylene oligomer.
As the base oil in the lubricating oil for continuously variable transmission, above-mentioned mineral oil and synthetic oil (compound) be can be used alone, or be used with any two or more of form of mixtures, and there is no the limitations to mixture ratio.
The sulfur content of base oil does not have special limitation.Sulfur content is preferably more than 0.2%, more preferably no more than 0.1%, most preferably not more than 0.05%.Additionally, it is preferred that using oily based on the mineral oil or synthetic oil by hydrofinishing, because such oil has the sulfur content no more than 0.005%, or substantially free of sulphur (being no more than 5ppm).
Aromatic content in base oil is not also particularly limited.The aromatic content of base oil is preferably 15% or lower, and more preferably 10% or lower, most preferably 5% or lower, this is to be used in the low friction characteristic that the lubricating oil of manual gear of vehicle keeps it for a long time.When aromatic content is more than 15%, base oil poorly deteriorates in terms of oxidation stability.
Here, aromatic content is defined as the amount of the aromatic fraction according to determined by ASTM D2549 " with the typical aromatic series of elution chromatography separation higher boiling oil and the standard method of test of non-aromatic fraction ".
The kinematic viscosity of base oil is not particularly limited.When lubricating oil is the lubricating oil for continuously variable transmission, the kinematic viscosity that base oil measures at 100 DEG C is preferably 2mm2/ s or higher, more preferably 3mm2/ s or higher, and be simultaneously preferably 20mm2/ s or lower, more preferable 10mm2/ s or lower, more preferred 8mm2/ s or lower.When the kinematic viscosity at 100 DEG C is lower than 2mm2When/s, lubricating oil can provide enough abrasion resistances and vaporizing property is poor.When movement concentration is more than 20mm2When/s, lubricating oil is difficult to show low friction characteristic and vaporizing property is degenerated, this is undesirable.About the present invention, it can be mixed to form a kind of mixture at least two base oil of unrestricted choice, in the mixture, the kinematic viscosity of single base oil can exceed above range, as long as mixture is fallen in above-mentioned preferred scope in the kinematic viscosity at 100 DEG C.
The viscosity index (VI) of base oil is not particularly limited, and when lubricating oil is used for continuously variable transmission, which is preferably 80 or higher, and more preferable 100 or higher, most preferably 120 or higher.The viscosity index (VI) for increasing base oil can provide superior low-temperature viscosity profiles and fuel economy for the lubricating oil for manual transmission.
Organic oxygen-containing compound is preferably selected from at least one compound for the group being made of unitary or polyalcohol, carboxylic acid, ether, ester and their derivative, and content is preferably based on the 0.05~3.0% of lubricating oil total amount.
Illustrate the example of alcohol below.
1.1 monohydric alcohol；
1.2 dihydric alcohol；
The alcohol of 1.3 ternarys or more member；
1.4 are selected from the alkylene oxide adduct of above-mentioned 1~3 alcohol；
1.5 are selected from above-mentioned 1.1~1.4 one or more mixtures.
Monohydric alcohol has a hydroxyl in the molecule, including the unitary alkylol for example with 1~40 carbon atom (wherein alkyl can be linear chain or branched chain), such as methanol, ethyl alcohol, propyl alcohol (1- propyl alcohol, 2- propyl alcohol), butanol (n-butyl alcohol, 2- butanol, 2- methyl-1-propyl alcohol, 2- methyl-2-propanol), amylalcohol (1- amylalcohol, 2- amylalcohol, 3- amylalcohol, 2-methyl-1-butene alcohol, 3- methyl-1-butanol, 3- methyl -2- butanol, 2- methyl -2- butanol, 2, 2- dimethyl -1- propyl alcohol), hexanol (1- hexanol, 2- hexanol, 3- hexanol, 2- methyl-1-pentene alcohol, 2- methyl -2- amylalcohol, 2- methyl -3- amylalcohol, 3- methyl-1-pentene alcohol, 3- methyl -2- amylalcohol, 3- methyl -3- amylalcohol, 4- Methyl-1-pentene alcohol, 4- methyl -2- amylalcohol, 2, 3- dimethyl-1-butanol, 2, 3- dimethyl -2- butanol, 3, 3- dimethyl-1-butanol, 3, 3- dimethyl -2- butanol, 2- ethyl-n-butyl alcohol, 2, 2- dimethyl butyrate alcohol), enanthol (1-heptanol, 2- enanthol, 3- enanthol, 2- methyl-1-hexanol, 2- methyl -2- hexanol, 2- methyl -3- hexanol, 5- methyl -2- hexanol, 3- ethyl -3- amylalcohol, 2, 2- dimethyl -3- amylalcohol, 2, 3- dimethyl -3- amylalcohol, 2, 4- dimethyl -3- amylalcohol, 4, 4- dimethyl -2- amylalcohol, 3- methyl-1-hexanol, 4- methyl-1-hexanol, 5- methyl-1-hexanol, 2- ethylpentanol), octanol (1- octanol , sec-n-octyl alcohol, 3- octanol, 4- methyl -3- enanthol, 6- methyl -2- enanthol, 2- ethyl -1- hexanol, 2- propyl -1- amylalcohol, 2, 4, 4- trimethyl -1- amylalcohol, 3, 5- dimethyl -1- hexanol, 2- methyl-1-enanthol, 2, 2- dimethyl -1- hexanol), nonyl alcohol (1 nonyl alcohol, 2- nonyl alcohol, 3, 5, 5- trimethyl -1- hexanol, 2, 6- 2,6-dimethyl-4-heptanol, 3- ethyl -2, 2- dimethyl -3- amylalcohol, 5- methyl-octanol etc.), decyl alcohol (1- decyl alcohol, 2- decyl alcohol, 4- decyl alcohol, 3, 7- dimethyl -1- octanol, 2, 4, 6- Trimethyl heptanols etc.), undecyl alcohol, lauryl alcohol, tridecanol, tetradecyl alchohol, pentadecanol, hexadecanol, heptadecanol, octadecyl alcolol (stearyl alcohol etc.), 19 Alcohol, eicosanol, two undecyl alcohols, tricosanol, tetracosanol；Unitary enol (wherein alkenyl group can be linear chain or branched chain, and double bond can be in any appropriate location) such as vinyl alcohol with 2~40 carbon atoms, propenyl, butenol, hexenol, matsutake alcohol, decenol, lanolin alcohol, oleic alcohol (oleyl alcohol etc.)；(wherein alkyl group can be linear chain or branched chain to unitary (alkyl) cycloalkyl alcohol with 3~40 carbon atoms, and alkyl and hydroxyl group can be in any appropriate locations), such as cyclopentanol, cyclohexanol, suberol, Lotka-Volterra circle system, methylcyclopentanol, methyl cyclohexanol, dimethyl cyclohexanol, ethyl cyclohexanol, cyclohexyl alcohol, butylcyclohexyl alcohol, dimethyl cyclohexanol, cyclopentyl carbinol, cyclohexyl ethyl alcohol (1- cyclohexyl ethyl alcohol, 2- cyclohexyl ethyl alcohol etc.), hexahydrobenzyl alcohol, cyclohexyl propyl alcohol (3- cyclohexyl propyl alcohol etc.), cyclohexyl butanol (4- cyclohexyl butanol etc.), butylcyclohexyl alcohol, 3, 3, 5, 5- tetramethyl-ring hexanol；(wherein alkyl can be linear chain or branched chain to (alkyl) aromatic radical alcohol, and alkyl and hydroxyl group can be in any appropriate locations) such as phenol, methylphenol (o-cresol, metacresol, paracresol), methyl phenol, ethyl -phenol, butylphenol, butyl methyl phenol (3 methy 6 tert butyl phenol etc.), xylenol, diethyl phenol, dibutylphenol (2, 6- DI-tert-butylphenol compounds, 2, 4- DI-tert-butylphenol compounds etc.), dibutylmethyl phenol (2, 6- di-tert-butyl-4-methy phenol etc.), dibutylethyl phenol (2, 6- di-t-butyl -4- ethyl -phenol etc.), tributyl phenol (2, 4, 6- tri-butyl-phenol etc.), naphthols (alpha-Naphthol, betanaphthol etc.), dibutyl naphthols (2, 4- di-t-butyl-alpha-Naphthol etc.), 6- (4- hydroxyl - 3,5- di-tert-butyl amido) -2,4- is to (thiocapryl) -1,3,5-triazines and their mixture.
Wherein, the more preferably alkyl or alkenyl alcohol of the linear chain or branched chain with 12~18 carbon atoms, such as oleyl alcohol and stearyl alcohol, because of the friction between the sliding surface that they can more effectively reduce the sliding part coated with hard carbon thin film and other any materials are formed, and their volatility are poor, therefore their friction reducing effect can be shown at high temperature.
Specifically there are two hydroxyl groups for tool in the molecule for glycol, including the alkyl or alkenyl glycol for example with 2~40 carbon atoms, (wherein alkyl or alkenyl can be linear chain or branched chain, the double bond of alkenyl can be in any appropriate location, and hydroxyl can also be in any appropriate location), such as ethylene glycol, diglycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, 1, 3-propanediol, 1, 4- butanediol, 1, 2- butanediol, 2- methyl-1, 3-propanediol, 1, 5- pentanediol, 1, 6- hexylene glycol, 2- Ethyl-2-Methyl -1, 3-propanediol, 2- methyl -2, 4- pentanediol, 1, 7- heptandiol, 2- methyl -2- propyl- 1, 3-propanediol, 2, 2- diethyl -1, 3-propanediol, 1, 8- ethohexadiol , 1,9- nonanediol, 2- butyl -2- ethyl -1,3-PD, 1,10- decanediol, 1,11- undecane, 1,12- dodecanediol, 1,13- tridecane diols, 1,14- tetradecane diols, 1,15- pentadecane diols, 1,16- hexadecane diol, 1,17- heptadecane diols, 1,18- octacosanol, 1,19- nonadecane glycol, 1,20- icosane diols；(alkyl) cycloalkanes glycol (wherein alkyl can be with linear chain or branched chain, and alkyl and hydroxyl can be in any appropriate locations), such as cyclohexanediol, methyl cyclohexane glycol；(wherein alkyl can be with linear chain or branched chain for binary (alkyl) aromatic alcohol with 2~40 carbon atoms, alkyl and hydroxyl can be in any appropriate locations), such as benzenediol (catechol etc.), methyl benzenediol, ethyl benzenediol, butyl benzenediol (p-tert-Butylcatechol etc.), dibutyl benzenediol (4, 6- di-tert-butyl resorcin etc.), 4, 4 '-is thio to (3 methy 6 tert butyl phenol), 4, 4 '-butylidenes are to (3 methy 6 tert butyl phenol), 2, 2 '-methylene are to (4- methyl-6-tert-butylphenol), 2, 2 '-is thio to (4, 6- di-tert-butyl resorcin), 2, 2 '-methylene are to (4- ethyl -6- tert-butyl phenol), 4, 4 '-methylene are to (2, 6- DI-tert-butylphenol compounds), 2, 2 ' (3,5- di-t-butyl -4- hydroxyl) propane, 4,4 '-cyclohexylenes are to (2,6- DI-tert-butylphenol compounds)；P-tert-butylphenol/formaldehyde condensate, p-tert-butylphenol/acetaldehyde condensate；And their mixture.
These, it is preferred to ethylene glycol, propylene glycol, neopentyl glycol, 1,4- butanediol, 1,5-PD, neopentyl glycol, 1,6- hexylene glycol, 2- methyl -2,4- pentanediol, 2- Ethyl-2-Methyl -1,3-PD, 1,7- heptandiol, 1,8- ethohexadiol, 1,9- nonanediol, 1,10- decanediol, 1,11- undecane, 1,12- dodecanediol, because they can more effectively reduce the friction between the sliding surface of the sliding part and any other material that are coated with hard carbon thin film.In addition, with at least 300, it is preferred that the high molecular weight hindered alcohols of 400 molecular weight, such as 2,6- di-t-butyl -4- (3,5- di-t-butyl -4- hydroxyphenyl) phenol is also preferably as they are difficult volatilization and highly heat-resistant at high temperature (such as under the sliding condition of internal combustion engine), and they can show their friction reducing effect well and assign lubricating oil superior antioxidative stabilizer.
The polyalcohol of ternary or more member refers to that those have three or more hydroxyls.Usually using trihydroxylic alcohol to ten yuan of alcohol, preferably trihydroxylic alcohol to hexahydroxylic alcohols.The example of these components is three methanol alkane, such as glycerol, methyltrimethylolmethane, trihydroxymethyl propane, three methanol butane, and erythrite, pentaerythrite, 1, 2, 4- butantriol, 1, 3, penta triol of 5-, 1, 2, 6- hexanetriol, 1, 2, 3, 4- erythrol, sorbierite, admitol, arabitol, xylitol, mannitol, and they polymer or condensate (such as, such as diglycerol, triglycerin, the glycerol dimer of four glycerol is to octamer, the trihydroxymethyl propane dimer of such as double trihydroxymethyl propanes is to octamer, the pentaerythrite dimer of such as dipentaerythritol is to octamer, sorbitan, such as sorbierite/glycerol condensate condensate (including intramolecular condensate, intermolecular condensate and self cooling condensate)).
The carbohydrate of such as xylose, arabinose, ribose, rhamnose, glucose, fructose, galactolipin, mannose, sorbose, cellobiose, mannose, isomaltose, trehalose and sucrose is also applicable.
Wherein, more preferably three to hexahydroxylic alcohols, such as glycerol, three methanol alkane (such as methyltrimethylolmethane, trihydroxymethyl propane, three methanol butane), pentaerythrite, 1,2,4-butanetriol, 1,3,5- penta triols, 1,2,6- hexanetriols, 1,2,3,4- erythrol, sorbierite, sorbitan, sorbierite/glycerol condensate, admitol, arabitol, xylitol, mannitol and their mixture；Moreover, more preferably glycerol, methyltrimethylolmethane, trihydroxymethyl propane, pentaerythrite, sorbitan and their mixture.Especially preferably oxygen content is at least 20%, preferably at least 30%, more preferably at least 40% polyalcohol.Higher than the viscosity that the polyalcohol of hexahydroxylic alcohols will greatly increase transmission oil.
Said components 1.4 include the alkylene oxide adduct of the alcohols selected from 1.1~1.3.Specifically, they be there is 2~6 carbon atoms, the alkylene oxide of preferably 2~4 carbon atoms or its polymer or copolymer by being added in alcohols, thus make the hydroxyl hydroxyl of alcohol be etherified or hydroxyl esterification and prepare.Alkylene oxide with 2~6 carbon atoms includes ethylene oxide, propylene oxide, 1,2- epoxy butane (α-epoxy butane), 2,3- epoxy butane (beta epoxide butane), 1,2- epoxy -1- methylpropane, 1,2- oxepane, 1,2- oxepane.These, it is preferred to ethylene oxide, propylene oxide and epoxy butane, because their antifriction are more effective；More preferably ethylene oxide and propylene oxide.
When using two or more different types of alkylene oxides here, the mode of oxyalkylene polymerization is not particularly limited, and group can be by atactic polymerization or block polymerization.When being added to alkylene oxide in the polyalcohol with 2~6 carbon atoms, all hydroxyls of polyalcohol can be added to, a part of hydroxyl can also be added to.
Illustrate the example of carboxylic acid below.
2.1 aliphatic monocarboxylic acids (fatty acid).
2.2 aliphatic polycarboxylic acid.
2.3 carbocyclic carboxylic acids.
2.4 heterocyclic carboxylic acid.
2.5 are selected from above-mentioned 2.1~2.4 two or more of mixtures.
Aliphatic carboxylic acid (fatty acid) refers to intermolecular there is carboxyl, (wherein including the representative examples of saturated aliphatic monocarboxylic acid for example with 1~40 carbon atom, representative examples of saturated aliphatic structure can be linear chain or branched chain), such as formic acid, acetic acid (acetic acid), propionic acid, butyric acid (butyric acid, isobutyric acid etc.), valeric acid (valeric acid, isovaleric acid, neopentanoic acid etc.), caproic acid, enanthic acid, octanoic acid, n-nonanoic acid, capric acid, undecanoic acid, lauric acid/dodecanoic acid (lauric acid), tridecanoic acid, tetradecylic acid (myristic acid), pentadecanoic acid, hexadecylic acid (palmitinic acid), heptadecanoic acid, stearic acid (stearic acid), nonadecanoic acid, 20 acid, heneicosoic acid, behenic acid, tricosanic acid, tetracosanoic acid, neocerotic acid, cerinic acid, carboceric acid, octacosanoic acid, motanic acid, triacontanoic acid；And, unsaturated aliphatic monocarboxylic acid with 1~40 carbon atom is (wherein, unsaturated aliphatic structure can be linear chain or branched chain, and unsaturated bond can be in any ideal position), such as acrylic acid, propiolic acid, butenoic acid (methacrylic acid, crotonic acid, iso-crotonic acid etc.), penetenoic acid, hexenoic acid, heptenoic acid, octenoic acid, nonenoic acid, decylenic acid, undecenoic acid, lauroleic acid, tridecylenic acid, tetradecenoic acid, pentadecylenic acid, gaidic acid, heptadecenoic acid, octadecenic acid (oleic acid), nonadecenoic acid, eicosenoic acid, two undecenoic acids, docosenoic acid, tricosenoic acid, nervonic acid, pentacosa alkene acid, ximenic acid, two heptadecenoic acids, two octadecenic acids, two nonadecenoic acids, lumequeic acid.
Aliphatic polycarboxylic acid include saturation with 2~40 carbon atoms or unsaturated aliphatic dicarboxylic acids (wherein, representative examples of saturated aliphatic or unsaturated aliphatic structure can be linear chain or branched chain, and unsaturated bond can be in any ideal position), such as ethanedioic acid (oxalic acid), malonic acid, succinic acid (succinic acid, methylmalonic acid etc.), glutaric acid (glutaric acid, ethyl malonic acid etc.), adipic acid (adipic acid etc.), pimelic acid, suberic acid (suberic acid etc.), azelaic acid (azalaic acid etc.), decanedioic acid, propylene diacid, butene dioic acid (maleic acid, fumaric acid etc.), glutaconate (citraconic acid, mesaconic acid etc.), hexene diacid, heptylene diacid, octendioic acid, nonendioic acid, decenedioic acid；Saturation or unsaturated tricarboxylic acids are (wherein, representative examples of saturated aliphatic or unsaturated aliphatic structure can be linear chain or branched chain, and unsaturated bond can be in any ideal position), such as three acid of propylene, three acid of butylene, three acid of amylene, three acid of hexene, three acid of heptene, three acid of octene, three acid of nonene, three acid of decene；And saturation or unsaturated quaternary carboxylic acid (wherein representative examples of saturated aliphatic or unsaturated aliphatic can be linear chain or branched chain, and unsaturated bond can be in any ideal position).
Carbocyclic carboxylic acids refer to has one or more carboxyls in carbocyclic ring, including for example, naphthenic base unitary with 3~40 carbon atoms, binary, ternary or quaternary carboxylic acid are (wherein, alkyl or alkenyl (if present) can be linear chain or branched chain, double bond (if present) can be in any ideal position, and the position of substituent group does not limit), such as hexamethylene monoacid, hexahydrotoluene monoacid, ethyl cyclohexane monoacid, propyl cyclohexane monoacid, butyl cyclohexane monoacid, pentylcyclohexane monoacid, hexyl hexamethylene monoacid, heptylcyclohexane monoacid, octylcyclohexane monoacid, cycloheptane monoacid, cyclooctane monoacid, trimethyl cyclopentane binary acid (camphoric acid etc.)；Aromatic series monoacid with 7~40 carbon atoms, such as benzene carboxylic acid (benzoic acid), methyl benzene carboxylic acid (toluic acid etc.), ethyl benzene carboxylic acid, propyl benzene carboxylic acid, benzene dicarboxylic acid (phthalic acid, M-phthalic acid, terephthalic acid (TPA) etc.), benzene tricarbonic acid (1,2,4- benzenetricarboxylic acid etc.), benzene tertacarbonic acid's (pyromellitic acid etc.), naphthalene-carboxylic acid (naphthoic acid etc.)；Aryl unitary, binary, ternary or quaternary carboxylic acid with 7~40 carbon atoms are (wherein, alkyl or alkenyl (if there is as substituent group) can be linear chain or branched chain, double bond (if any) can be in any ideal position, and substituent group quantity and position do not limit), such as phenyl propiolic acid (hydratropic acid), phenylacrylic acid (atropic acid, cinnamic acid etc.), salicylic acid has 1~30 carbon atom, the alkyl salicylate containing one or more alkyl.
Heterocyclic carboxylic acid, which refers to, one or more carboxyls in those molecules, including for example those there are 5~40 carbon atoms, such as furancarboxylic acid, thio benzene carboxylic acid, picolinic acid (niacin, nicotimine acid etc.).
Illustrate the example of ether below.
3.1 saturations or unsaturated aliphatic ether.
3.2 aromatic oxide.
3.3 cyclic ethers.
The mixture of 3.4 two or more in above-mentioned 3.1~3.3.
Aliphatic unitary ether specifically refers to the saturated or unsaturated fatty ether with 1~40 carbon atom (wherein, saturation or unsaturated aliphatic structure can be linear chain or branched chain, and unsaturated bond can be in any ideal position), such as dimethyl ether, diethyl ether, di-n-propyl ether, diisopropyl ether, butyl oxide, diisobutyl ether, two n-amylethers, isoamyl ether, two hexyl ethers, two heptyl ethers, dioctyl ether, two nonyl ethers, didecyl ether, two (undecyl) ethers, two (dodecyl) ethers, two (tridecyl) ethers, two (myristyl) ethers, two (pentadecyl) ethers, two (cetyl) ethers, two (heptadecyl) ethers, two (octadecyl) ethers, two (nonadecyl) ethers, two (eicosyl) ethers, methyl ethyl ether, methyl n-propyl ether, methyl isopropyl ether, methyl-isobutyl ether, methyl tertiary butyl ether(MTBE), methyl is just Amyl ether, methyl isoamyl ether, ethyl n-propyl ether, ethyl isopropyl ether, ethyl isobutyl ether, ethyl tert-butyl ether (ETBE), ethyl n-pentyl ether, ethyl isoamyl ether, vinethene, diallyl ether, methyl vinyl ether, methallyl ether, ethyl vinyl ether, ethyl allyl ether.
Specifically, aromatic oxide includes such as methyl phenyl ethers anisole, phenetole, diphenyl ether, benzyl ether, benzyl phenyl ether, Alpha-Naphthyl ether, β-naphthalene ether, polyphenylene oxide, perfluoroether；Also, they can have a saturated or unsaturated group (wherein, saturation or unsaturated group can be linear chain or branched chain, and unsaturated bond can be located at any ideal position, and the quantity of substituent group and position do not limit).Preferably, they are under running conditions, particularly at room temperature liquid.
Specifically, cyclic ethers is that those have 2~40 carbon atoms, including such as ethylene oxide, propylene oxide, oxetanes, tetrahydrofuran, oxinane, dioxanes, glycidol ether；Moreover, they have a saturation or unsaturated group, a carbocyclic ring, or a carbocyclic ring containing saturation or unsaturated aliphatic is (wherein, saturation or unsaturated group can be linear chain or branched chain, and unsaturated bond can be in any ideal position, and the number and location of substituent group do not limit).
Illustrate the example of ester below.
The ester of 4.1 aliphatic monocarboxylic acids (fatty acid).
The ester of 4.2 aliphatic polycarboxylic acids.
The ester of 4.3 carbocyclic carboxylic acids.
The ester of 4.4 heterocyclic carboxylic acids.
The alkylene oxide adduct of 4.5 alcohol or ester.
4.6 are selected from the mixture of above-mentioned 4.1~4.5 any component.
Above-mentioned 4.1~4.5 ester can be the full ester that wherein hydroxyl and carboxyl are all esterified or the partial ester that some of hydroxy or carboxy are still kept intact.
Above-mentioned 4.1 component is the ester selected from above-mentioned aliphatic monocarboxylic acid (fatty acid) and one or more polyalcohols selected from above-mentioned unitary, binary, ternary or more member, it includes a kind of ashless aliphatic ester friction improver.This is ashless, and aliphatic ester friction improver is the aliphatic ester with 6~30, preferably 8~24, the linear or branched alkyl group of more preferable 10~20 carbon atoms, it includes the ester with the fatty acid and aliphatic monobasic alcohol or aliphatic polyol of abovementioned alkyl.Fatty acid mentioned here is aliphatic monocarboxylic acid.And specifically, it is preferable to the example of ester be monoolein, diolein, anhydro sorbitol monooleate, sorbitan dioleate, and the like.
In addition to ashless aliphatic ester friction improver, component 4.1 includes the aliphatic ester containing linear or branched alkyl group with 1~5 carbon atom or 31~40 carbon atoms.Their example is the ester with the fatty acid and aliphatic monobasic alcohol or aliphatic polyol of abovementioned alkyl.
Among above-mentioned, the kinematic viscosity at 100 DEG C is in 1~100mm2It can be used as the base oil of lubricating oil those of between/sec, and usually differentiated with above-mentioned aliphatic ester friction improver.Their example is polyol ester, such as by with 3~40, preferably 4~18, the ternary of more preferable 4~12 carbon atoms or higher polyalcohol, especially with the polyalcohol of neopentyl structure, the above-mentioned monocarboxylic monoesters or mixed ester with 1~40, preferably 4~18, more preferable 6~12 carbon atoms is selected from one or more, and the adduct of they and the alkylene oxide being added thereto, such as trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythrite 2 ethyl hexanoic acid ester, pentaerythrite pelargonate.They can be the full ester that wherein hydroxyl and carboxyl are all esterified, or the partial ester that part of hydroxy or carboxy is still kept intact.But they are preferably full ester.The hydroxyl value of ester is generally up to about 100mg KOH/g, is preferably up to 50mg KOH/g, is more preferably up to 10mg KOH/g.
Preferably, kinematic viscosity of the base oil of lubricating oil at 100 DEG C is in 2~60mm2Between/sec, more preferably in 3~50mm2Between/sec.
Component 4.2 is one or more esters selected from above-mentioned aliphatic polybasic acids and one or more polyalcohols selected from above-mentioned unitary, binary, ternary or more member.Its preferred embodiment is selected from 2~40, it is preferred that 4~18, one or more polybasic carboxylic acids of the dicarboxylic acids of more preferable 6~12 carbon atoms, with one or more selected from 4~40, it is preferred that 4~18, the ester of the monohydric alcohol of more preferable 6~14 carbon atoms, such as dibutyl maleate, glutamic acid double tridecyl ester, the double 2- ethylhexyls of adipic acid, adipic acid diiso decyl ester, adipic acid double tridecyl ester, the double 2- ethylhexyls of decanedioic acid, and the copolymer of these esters (such as dibutyl maleate) and the poly alpha olefin with 4~16 carbon atoms；And the ester of alpha-olefin adduct and acetic anhydride and the like and the alcohol with 1~40 carbon atom.In above compound, those at 100 DEG C kinematic viscosity in 1~100mm2The base oil that may be used as lubricating oil between/sec.
Component 4.3 is one or more selected from above-mentioned carbocyclic carboxylic acids and one or more esters selected from above-mentioned unitary, binary, ternary or higher polyalcohol.Its preferred embodiment is aromatic carboxylic acid ester, such as phthalic acid ester, benzenetricarboxylic acid ester, pyromellitic ester, salicylate.In above-mentioned ester, those at 100 DEG C kinematic viscosity in 1~100mm2The base oil that may be used as lubricating oil between/sec.
Component 4.4 is one or more selected from above-mentioned heterocyclic carboxylic acid and one or more esters selected from above-mentioned unitary, binary, ternary or higher polyalcohol.In these esters, those at 100 DEG C kinematic viscosity in 1~100mm2The base oil that may be used as lubricating oil between/sec.
Component 4.5 includes by the way that a kind of alkylene oxide, the then prepared ester of esterification, and the adduct prepared and alkylene oxide is added in the ester selected from said components 4.1~4.4 are added in above-mentioned unitary, binary, ternary or higher polyalcohol one or more.In the compound, those at 100 DEG C kinematic viscosity in 1~100mm2The base oil that may be used as lubricating oil between/sec.
The derivative of above-mentioned organic oxygen-containing compound specifically includes, such as those a kind of are prepared by vulcanizing selected from above-mentioned alcohol, carboxylic acid, ester and ether；By halogenation (fluorination, chlorination), it is prepared for those；It and acid, such as the reaction product of sulfuric acid, nitric acid, boric acid, phosphoric acid or their ester or metal salt；And the reaction product of it and metal, metal-containing compound or amine compounds.
These, it is preferred to selected from one of alcohol and carboxylic acid and their derivative or a variety of and amine compounds reaction products (such as Mannich reaction products, acylate, amide).
Amine compounds mentioned here include ammonia, monoamine, diamine and polyamine.More specifically, their example is ammonia；Containing 1~30 carbon atom, alkylamine with alkyl group is (wherein, alkyl group can be linear chain or branched chain), such as methylamine, ethamine, propylamine, butylamine, amylamine, hexylamine, heptyl amice, octylame, nonyl amine, decyl amine, heptadecyl-amine, dodecyl amine, tridecyl amine, tetradecylamine, pentadecyl amine, cetylamine, heptadecylamine (HDA), octadecylamine, stearylamine, dimethylamine, diethylamine, di-n-propylamine, dibutyl amine, diamylamine, dihexylamine, two heptyl amices, dioctylamine, nonyl amine, didecylamine, double heptadecyl-amines, double dodecyl amines, diamin, double tetradecylamines, double pentadecyl amines, double cetylamines, double heptadecylamine (HDA)s, double octadecylamines, Methylethyl amine, methyl-propyl amine, methyl butyl amine, ethyl propyl amine, N-Ethylbutylamine, and propylbutylamine；Alkenyl amine (wherein, alkenyl can be linear chain or branched chain) containing 2~30 carbon atoms, with alkenyl group, such as vinylamine, allylamine, butenylamine, octene amine and oleyl amine；Alkanolamine (wherein, alkanol groups can be linear chain or branched chain) containing 1~30 carbon atom, with alkanol groups, such as carbinolamine, ethanol amine, Propanolamine, butanolamine, amylalcohol amine, hexanol amine, enanthol amine, octanol amine, nonyl alcohol amine, methanol/ethanol amine, methanol Propanolamine, methanol butanolamine, ethanol propanol amine, ethanol and butanol amine and propyl alcohol butanolamine；Containing 1~30 carbon atom, with the alkylene diamines of alkylene group, such as methylene diamine, ethylene diamine, trimethylene diamine and butylene diamine；Polyamine, such as diethylenetriamines, trien, tetren, penten；Derived from above-mentioned monoamine, diamine or polyamine and further comprise one with 8~20 carbon atoms alkyl or alkenyl group derivative; such as undecyl diethylamine; undecyl diethanol amine; dodecyl Propanolamine; octadecyldiethanol amine; octadecyl propylene diamine, octadecanoyl tetraethylenepentamine；Heterocyclic compound, such as N- ethoxy oil-based imidazoline (N-hydroxyethyloleylimidazoline)；The alkylene oxide adduct of these compounds and their mixture.
In those nitrogenous compounds, the preferably aliphatic amine of the alkyl or alkenyl group (they can be linear chain or branched chain) with 10~20 carbon atoms, such as decyl amine, lauryl amine, tridecyl amine, heptadecyl amine, octadecylamine (octadecylamine), octadecenyl amine and octadecylamine (stearylamine).
In the derivative of oxygen-containing organic compound, preferably with the carbamide of 8~20 carbon atoms, such as oleamide.
The example of aliphatic amine compound is that each contains C6~C30, preferably C8~C24, more preferable C10~C20The hydrocarbon chain of linear chain or branched chain or the aliphatic amine compound of group.When the carbon atom number in alkane chain is not in 6~30 ranges, lubricating oil is possible to that expected abundant friction reducing effect cannot be generated.
C6~C30The specific example of linear chain or branched chain hydrocarbon chain includes: alkyl, such as hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl, eicosyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, cerul, heptacosane base, octacosyl, nonacosyl, melissyl；And alkenyl, such as hexadecene base, heptadecene base, octadecene base, 19 carbene bases, eicosylene base, heneicosene base, two dodecenyl succinics, tricosene base, tetracosa carbon alkenyl, ppentacosene base, cerotene base, cerotene base, two octadecene bases, 29 carbene bases, melene base.Abovementioned alkyl and alkenyl include all possible isomers.In addition, the position of alkenyl is free.
Aliphatic amine compound can be by taking aliphatic mono and its alkylene oxide adduct, aliphatic polyamine, imidazolinium compounds and its derivative as an example.The specific example of above-mentioned aliphatic amine includes: aliphatic amine compound, such as lauryl amine, dodecyl diethylamide, dodecyl diethanol amine, dodecyl hydramine, cetylamine, octadecylamine, octadecyl tetraethylenepentamine, octadecylamine, oil base propylene diamine, oil base diethanol amine and N- ethoxy oleyl imidazoles alkynes (N-hydroxyethyloleylimidazolyne)；Above-mentioned aliphatic amine (C6~C28Alkyl or alkenyl amine) with the adduct of alkylene oxide, such as N, N- polyoxyalkylene-N- alkylamine；And by above-mentioned aliphatic amine and C2~C30Monocarboxylic acid (such as fatty acid) or C2~C30The sour modified compound that polybasic carboxylic acid (such as ethanedioic acid, phthalic acid, benzenetricarboxylic acid and pyromellitic acid) reaction is in and/or all or part of remaining amino of amidation and/or imino group are to prepare.About the present invention, bis- polyethylene oxide-N- oleyl amine of N, N- be it is preferable to use.
Amount (content) for contained aliphatic amine compound in the lubricant oil composite of manual transmission is not particularly limited, and is preferably based on the 0.05~3.0% of lubricating oil total amount, and more preferable 0.1~2.0%, most preferably 0.5~1.4%.When the content of aliphatic ester friction improver and/or aliphatic amine friction improver is lower than 0.05%, it is possible to which lubricating oil cannot generate enough friction reducing effects.When the content of aliphatic ester friction improver and/or aliphatic amine friction improver is more than 3.0%, lubricating oil generates enough friction reducing effects, but undesirably deteriorates in terms of storage stability and compatibility so as to cause precipitating.
In addition, preferably including polybutenyl succinic acid imide and/or its derivative as ashless dispersant for continuously variable transmission oil of the invention or the transmission oil for continuously variable transmission.The imido specific example of the polybutenyl succinic that the present invention is applicable in includes the following general formula (1) and the compound that (2) indicate:
In structural formula (1) and (2), n is the integer between 1~5, and preferably 2~4 to obtain good cleaning effect.In addition, PIB indicates polybutylene-based derived from polybutene.Polybutene can obtain 900~3500 in the presence of boron fluoride or aluminum chloride catalyst, by polybutene, polymerize the isobutene of high-purity in a manner of preferably 1000~2000 number-average molecular weights or the mixture of 1- butylene and isobutene and be prepared.When the number-average molecular weight of polybutene is less than 900, it is possible to clean enough effect cannot be obtained.When the number-average molecular weight of polybutene is more than 3500, polybutene may undesirably deteriorate in terms of low temperature flow.In the imido production of polybutenyl succinic, polybutene can use after removing Trace Fluoride and the remaining purification of chlorine by any proper treatment (such as absorption method or ablution), these Trace Fluorides and chlorine residual are caused by producing catalyst by above-mentioned polybutene.The residual quantity of fluorine and chlorine is preferably controlled in 50ppm or lower, more preferable 10ppm or lower, most preferably 1ppm or lower.
The production of polybutylene succinimide is not particularly limited.Such as, polybutenyl succinic acid imide can be reacted with maleic anhydride by making the chloride of above-mentioned polybutene or having removed the remaining polybutene of fluorine chlorine at 100~200 DEG C to generate polybutylene succinate, the polybutylene succinate that then makes and polyamine (such as diethylenetriamines, trien, tetren, penten) it reacts to be made.
Polybutenyl succinic imide derivative can be by taking the modified compound of boron modification and acid as an example, they are that the polybutenyl succinic acid imide of structural formula (1) and (2) reacts in boron compound or oxygen-bearing organic matter and/or prepared by amidation remnants amino and/or imino group and by making.Wherein, boracic polybutenyl succinic acid imide, especially boracic two (polybutylene-based) succinimide be it is preferable to use.
Above-mentioned boron compound can be boric acid, borate or borate.The specific example of boric acid includes ortho-boric acid, metaboric acid and to boric acid.The specific example of borate includes ammonium salt, such as ammonium metaborate, tetraboric acid ammonium, ammonium pentaborate and eight ammonium borates.The specific example of borate includes: boric acid and alkylol (preferably C1~C6Alkylol) ester, such as one methyl esters of boric acid, trimethyl borate, trimethylborate, one ethyl ester of boric acid, boric acid diethylester, triethyl borate, one butyl ester of boric acid, boric acid dibutyl ester, butyl borate.Here, the content ratio (B/N) of boron and nitrogen in boracic polybutenyl succinic acid imide is usually 0.1~3, preferably 0.2~1 in mass.
Above-mentioned oxygenatedchemicals is for following: C1~C30Monocarboxylic acid, such as formic acid, acetic acid, glycolic, propionic acid, lactic acid, butyric acid, valeric acid, caproic acid, enanthic acid, octanoic acid, n-nonanoic acid, capric acid, undecanoic acid, lauric acid/dodecanoic acid, tridecanoic acid, tetradecylic acid, pentadecanoic acid, hexadecylic acid, heptadecanoic acid, stearic acid, oleic acid, nonadecanoic acid and 20 acid；C2~C30Dicarboxylic acids, such as ethanedioic acid, phthalic acid, benzenetricarboxylic acid and pyromellitic acid and its acid anhydrides and ester；C2~C6Alkylene oxide；And hydroxyl (poly-) alkylidene oxide carbonic ester.
The amount of the polybutenyl succinic acid imide and/or its derivative that are added in lubricating oil is not particularly limited, and the gross mass for being preferably based on transmission oil is 0.1~15%, more preferable 1.0~12%.When the amount of polybutenyl succinic acid imide and/or its derivative is lower than 0.1%, it is possible to enough cleaning effects cannot be obtained.It is uneconomical when the amount of polybutenyl succinic acid imide and/or its derivative is more than 15%.In addition, the amount of so big polybutenyl succinic acid imide and/or its derivative is easy to cause the deterioration of breaking ability.
As discussed above, about the present invention, lubricating oil shows extraordinary low friction characteristic in the case where can be between the sliding surface of the hard carbon thin film for such as DLC and relative component.For performance needed for improving the lubricating oil (composition) for continuously variable transmission, lubricating oil can contain other additives, such as metal detergent, antioxidant, viscosity index improver, other friction improvers in addition to above-mentioned aliphatic ester friction improver and/or aliphatic amine friction improver, other ashless dispersants in addition to above-mentioned polybutenyl succinic acid imide and/or its derivative, antiwear agents or extreme pressure (extreme-pressure) additive (reagent), antirust agent, nonionic surface active agent, demulsifying agent, metal deactivator, and/or defoaming agent when for internal combustion engine.These additives can use individually or in the form of two or more mixtures, to meet required transmission oil performance.
Metal detergent can be the conventionally used any metal cleaning immunomodulator compounds of lubricating oil.Specific example for metal detergent related to the present invention includes the sulfonate, phenates and salicylate of alkali or alkaline earth metal；And its two or more of mixtures.The example of alkali metal includes sodium (Na) and potassium (K), and the example of alkaline-earth metal includes calcium (Ca) and magnesium (Mg).Related to the present invention, sodium sulfonate and calcium, sodium phenate and calcium and sodium salicylate and calcium are applicable.The total base number and amount of metal detergent can be selected according to the performance of required lubricating oil.The total base number of metal detergent is measured according to ISO 3771 " measurement of base number-perchloric acid potentiometric titration " with perchloric acid, usually 0~500mgKOH/g, preferably 150~400mgKOH/g.The amount of metal detergent is typically based on the 0.1~10% of lubricating oil gross mass.
Any antioxidant that antioxidant can be commonly used in lubricating oil.Applicable antioxidant related to the present invention includes: phenolic antioxidant, such as 4, and 4 "-methylene are to (2,6- DI-tert-butylphenol compounds)-and octadecyl -3- (3,5- di-t-butyl -4- hydroxy phenyl) propionate；Amino-type antioxidant, such as phenyl-α-naphthylamine, alkyl phenyl-alpha-naphthylamine and alkyl diphenylamine；And its two or more of mixtures.The amount of antioxidant is typically based on the 0.01~5% of lubricating oil gross mass.
Viscosity index improver can it is following for: non-dispersive type viscosity index improver, such as one or more monomers of the hydride selected from base acrylic acid and copolymer；And Dispersant viscosity index improver, such as the copolymer (including nitrogen compound) of methacrylate.Also the copolymer (such as propylene, 1- butylene and 1- amylene) and its hydride of ethylene and alpha-olefin can be used, polyisobutene and its hydride, the copolymer of the hydrogenated copolymer of styrene and alkadienes, styrene and maleic anhydride and alkyl styrenes is as viscosity index improver.
The molecular weight needs of viscosity index improver are selected according to shear stability.For example, the number-average molecular weight of viscosity index improver, for distributed or non-dispersive type polymethacrylates preferably between 5,000~1,000,000, more preferably between 100,000~800,000；For polyisobutene and its hydride between 800~5,000；For ethylene/alpha-olefin copolymer and its hydride between 800~300,000, preferably between 10,000~200,000.Above-mentioned viscosity index (VI) is improved compound and can be used individually or in the form of two or more mixtures.It is 0.1~40.0% that the amount of viscosity index improver, which is preferably based on lubricating oil gross mass,.
Friction improver in addition to above-mentioned aliphatic amine compound can be by taking the metal friction modifier of such as borate, the Ashless friction modifiers of higher alcohols and fatty ether and such as molybdenum dithiophosphate, dithiocarbonic acids molybdenum and molybdenum disulfide as an example.
Ashless dispersant in addition to above-mentioned polybutenyl succinic acid imide and/or its derivative can illustrate such as: each has 900~3, the polybutylene-based polybutylene-based aniline and polybutene amine of 500 number-average molecular weights has the polybutenyl succinic acid imide and its derivative of the number-average molecular weight lower than 900.
Anti-friction liniment or EP agent can illustrate such as: disulphide, sulfurized fatty and oil, olefin sulphide, have one~tri- C2~C20The amine salt of the phosphate of alkane group, thiophosphate, phosphite ester, thiophosphite and these esters.
Antirust agent can illustrate such as alkyl benzene sulfonic acid ester, dinonyl naphthalene, the ester of alkenyl succinic acid and the ester of polyalcohol.
Nonionic surface active agent and demulsifying agent can illustrate such as non-ionic polyene ethyl glycol surfactant, such as polyoxyethylene alkylether, polyethylene oxide base alkyl phenyl ether and polyethylene oxide base alkyl naphthyl ether.
Metal deactivating dose can illustrate such as imidazolinium compounds, pyrimidine derivatives, thiazole and benzotriazole.Defoaming agent can illustrate such as siloxanes, fluorosilicone and fluoroalkyl ether.
Each in friction improver in addition to aliphatic ester friction improver and/or aliphatic amine friction improver, ashless dispersant, antiwear agents or EP agent in addition to polybutenyl succinic acid imide and/or its derivative, antirust agent and demulsifying agent usually accounts for the 0.01~5% of lubricating oil gross mass, and metal is subtracted deactivator and is included with 0.0005~1% based on lubricating oil gross mass.
Experiment 1
The present invention is more specifically described with reference to the following examples and comparative example, but embodiment and comparative example are not intended to limit the scope of the invention.
[manufacture of sliding part]
Use carburizing SCM420 stainless steel as basis material.It is formed block and ring, and it is that LFW-1 is tested and limited (referring to " LFW-1 experimental condition " cited below) that size, which is by Falex company,.
Block:
The sliding block of SCM420 stainless steel is carburizing and is tempered at low temperature, and their sliding surface strap (wrapping tape) polishing and polishing is so that surface roughness Ra is 0.03 μm.The surface of so treated sliding block is optionally covered with one layer of plating material through PVD or CVD processing to apply, to form the coating (hard carbon thin film) that a layer thickness is 1.1 μm in the upper surface of it, then it is polished and is polished with strap again, make 0.03 μm of surface roughness Ra.
Ring:
The ring of SCM420 stainless steel is carburizing and is tempered at low temperature, and their polishing of sliding surface strap and polishing is so that surface roughness Ra is 0.04 μm.The Details: SUMMARY of the block and ring that so prepare is in rear subordinate list 1.
[preparation of CVTF composition]
Preparing a kind of paraffin base mineral oil, (kinematic viscosity at 100 DEG C is 4.3mm2/ sec) based on oil.It is properly added aliphatic ester, aliphatic amine, amide or alcohol friction improver and CVTF packaging additive and polymethacrylates, wherein to prepare CVTF composition.The CVTF composition obtained as in embodiment 1-1~1-11 and comparative example 1-1 and 1-2 and above-mentioned sliding area are combined.The details of these embodiments and comparative example indicates in rear subordinate list 2.
In table 2, aliphatic ester is monoglyceride；Commercial product CVTF is Nissan genuine oily " NS-2 ", which includes a kind of friction improver；And CVTF packaging additive contains the mixture (but without friction improver) of detergent dispersant, antioxidant, antiwear agents, antirust agent, pour-point depressant, defoaming agent and the like.
[performance evaluation]
According to LFW-1 test method as defined in ASTM D2714, test sample under the test condition mentioned below.Its coefficient of friction is calculated by frictional force of each sample after on-test in 60 minutes.Obtained result is shown in Table 4 below.LFW-1 test condition:
Test equipment: Falex ring-block (Block-on-Ring) wear test machine, the production of Falex company；
Sample: block (Falex type H-60)
Ring (Falex type S-10)
Sliding speed: 0.26 meter per second
Load: 222.5N；
Oil temperature: 110 DEG C；And
Testing time: 60 minutes.
By table 2 it is appreciated that being used in combination friction improver and DLC (α-C) brings friction reducing effect than only using DLC (α-C:H) or without coating the case where is bigger.It is now believed that embodiment 3-6 is best in terms of friction reducing effect.
As described above, in this embodiment, on the position that a certain amount of continuously variable transmission fluid composition is present in the sliding part coated with hard carbon thin film between the relative component that is formed by any material.Therefore, the low friction sliding part that present embodiment provides a kind of in continuously variable transmission, its advantages are good wear resistances, are provided for buncher fluid composition.
Second embodiment
By second embodiment of the low friction sliding part discussed in speed changer according to the present invention.
The sliding part that low friction sliding part in automatic transmission is at least one to be in slidable contact with each other in continuously variable transmission oil or can be referred to fluid (composition) of " ATF (composition) " in the presence of.The low friction sliding part has a sliding area, and the sliding surface of the sliding area is coated with hard carbon thin film.Automatic transmission fluid (lubricating oil) is used as Ashless friction modifiers containing at least one of organic oxygen compound and aliphatic amine compound.By automatic transmission fluid, at least one sliding surface of sliding part is coated by hard carbon thin film, and therefore sliding part can be in slidable contact with each other with the friction far below routine techniques.The example of low friction sliding part is gear in continuously variable transmission, rotary shaft, the component of bearing and the like.Fig. 2 indicates a part of a tooth 10A for a gear in automatic transmission.Gear teeth 10A includes the basis material 12A coated on sliding surface by hard carbon thin film 14A.
Hard carbon thin film by carbon atom and amorphous DLC (diamond-like-carbon) material formed by for example mainly being formed.The DLC material has diamond (SP between carbon in bonding mode3Bonding) structure and/or graphite (SP2Bonding) structure.More specifically, hard carbon thin film by be made of carbon not hydrogeneous amorphous carbon (α-C), hydrogeneous amorphous carbon (α-C:H) or formed as part thereof of metal carbides or metal carbon (MeC) containing metal element of titanium (Ti) or molybdenum (Mo).
As the hydrogen content in hard carbon thin film increases, coefficient of friction increases.Therefore in the present invention it is essential that the hydrogen content upper limit in hard carbon thin film is 20 atom %.In order to sufficiently reduce coefficient of friction of the lubricating oil in sliding and obtain stable sliding properties, the hydrogen content in hard carbon thin film is preferably more than 10 atom %, more preferably no more than 0.5 atom %.
Hard carbon thin film with so low hydrogen content is obtained by not using the PVD method of hydrogen and/or hydrogen-containing compound substantially, such as sputtering method or ion electroplating method.In this case, it is preferred that in baking reactor and the tool for being used to support basis material, and sufficiently cleaning basis material surface to reduce the hydrogen content in hard carbon thin film, and in film formation operation use not hydrogeneous gas when, carry out the film formation operation of hard carbon thin film.
Hard carbon thin film is formed on the surface of basis material.Since the film thickness of hard carbon thin film is fairly small, the substrate material surface roughness before hard carbon thin film is formed greatly affects the surface roughness of the hard carbon thin film being formed on substrate material surface.Therefore, before basis material is not coated by hard carbon thin film, surface roughness (center line average roughness) Ra of basis material is preferably no greater than 0.1 μm.If the Film roughness of basis material is more than 0.1 μm, the convex portion as caused by the surface roughness of hard carbon thin film increases local Hertz ' the s contact pressure to relative component, thus induction of the formation in crack in hard carbon thin film.Surface roughness Ra JIS (Japanese Industrial Standards) B 0601 (: R is construed in 2001)a75。
Hard carbon thin film preferably has the thickness of surface hardness or micro-vickers hardness (Hv) and range between 0.3~2.0 μm in measure under 10g load application, range between 1000~3500.If the surface hardness and thickness of hard carbon thin film have exceeded above range, the abrasion that hard carbon thin film will then occur in film hardness (Hv) less than 1000 and when thickness is less than 0.3 μm, the removing of hard carbon thin film will be prone to when surface hardness (Hv) is more than 3500 and thickness is more than 2.0 μm.
The sliding part that the low friction sliding part of the present embodiment is used as in automatic transmission is particularly effective, the sliding part of the automatic transmission has respective slidingsurface, in the presence of the automatic transmission fluid that these surfaces provide between accessible sliding surface, the sliding contact between the sliding surface of the relative component formed by iron-based material or aluminium alloy.The automatic transmission fluid of the present embodiment does not include continuously variable transmission, operates discontinuous or step-type speed changer therefore, it is intended that having obtained speed and having changed.
In the following, will be discussed for the automatic transmission fluid of continuously variable transmission.
The automatic transmission gear shift device oil preferably comprises a kind of base oil and at least one of organic oxygen-containing compound and aliphatic amine compound as Ashless friction modifiers.It must be noted that in slidingsurface by there are when transmission oil, can obtain very superior low friction characteristic at hard carbon thin film coating.
Base oil, organic oxygen-containing compound and the aliphatic amine compound of automatic transmission fluid are identical as used in first embodiment continuously variable transmission oil.In addition, automatic transmission fluid in the present embodiment can contain other components in addition to base oil, organic oxygen-containing compound, aliphatic amine compound used in the continuously variable transmission oil.
Experiment 2
The present invention is more specifically described with reference to the following examples and comparative example, but embodiment and comparative example are not intended to limit the scope of the invention.
[manufacture of sliding part]
Use carburizing SCM420 stainless steel as basis material.It is formed block and ring, and it is that LFW-1 is tested and limited (referring to " LFW-1 experimental condition " cited below) that size, which is by Falex company,.
Block:
The sliding block of SCM420 stainless steel is carburizing and is tempered at low temperature, and their polishing of sliding surface strap and polishing is so that surface roughness Ra is 0.03 μm.The surface of so treated sliding block is optionally through PVD or CVD processing to coat one layer of plating material, to form the coating (hard carbon thin film) that a layer thickness is 1.1 μm in the upper surface of it, then it is polished and is polished with strap again, make 0.03 μm of surface roughness Ra.
Ring:
The ring of SCM420 stainless steel is carburizing and is tempered at low temperature, and their polishing of sliding surface strap and polishing is so that surface roughness Ra is 0.04 μm.The Details: SUMMARY of the sliding block and ring that so prepare is in rear subordinate list 3.
[preparation of ATF composition]
Preparing a kind of paraffin base mineral oil, (kinematic viscosity at 100 DEG C is 4.3mm2/ sec) based on oil.It is properly added aliphatic ester, aliphatic amine, amide or alcohol friction improver and ATF packaging additive and polymethacrylates, wherein to prepare ATF composition.The ATF composition obtained as in embodiment 2-1~2-11 and comparative example 2-1 and 2-2 and above-mentioned sliding area are combined.The details of these embodiments and comparative example indicates in rear subordinate list 4.
In table 4, aliphatic ester is monoglyceride；Commercial product ATF is Nissan genuine oily " Matic-J ", which includes a kind of friction improver；And ATF packaging additive contains a kind of friction improver.
[performance evaluation]
It is tested according to LFW-1 as defined in ASTM D2714, test sample under the test condition mentioned below.Its coefficient of friction is calculated by frictional force of each sample (block) after on-test in 60 minutes.Obtained result is shown in Table 4 below.LFW-1 test condition:
Test equipment: Falex ring-block wear test machine, the production of Falex company；
Sample: block (Falex type H-60)
Ring (Falex type S-10)；
Sliding speed: 0.26m/sec；
Load: 222.5N；
Oil temperature: 110 DEG C；And
Testing time: 60 minutes.
By table 4 it is appreciated that being used in combination friction improver and DLC (α-C) brings friction reducing effect than only using DLC (α-C:H) or without coating the case where is bigger.It is now believed that embodiment 2-6 is best in terms of friction reducing effect.
As described above, in this embodiment, on the position that a certain amount of continuously variable transmission fluid composition is present in the sliding part coated with hard carbon thin film between the relative component that is formed by any material.Therefore, the low friction sliding part that present embodiment provides a kind of in continuously variable transmission, its advantage is that its friction is very low and stablizes, it has good wear resistance, and is provided for automatic transmission fluid composition.
Although hard carbon thin film (such as diamond class C film) is described as being prepared with PVD process in embodiments, it is clear that hard carbon thin film can also be prepared with CVD technique.
Japanese patent application P2003-208366 (applies) on August 22nd, 2003, P2003-208368 (applies for) that the full content of P2004-230038 (applying on August 6th, 2004) and P2004-230039 (applying on August 6th, 2004) are by reference to and including herein on August 22nd, 2003.
Although describing the present invention above by reference to certain embodiments of the present invention and example, the present invention is not limited in the embodiment above and example.According to the above instruction, those skilled in the art will expect the modification and variation of the embodiment above and example.The scope of the present invention is defined with reference to following claim.
Table 1
Sliding part type Ring Block
Basis material (matrix) Surface roughness Ra, μm Surface hardness HRC Basis material (matrix) Surface roughness Ra, μm Surface hardness HRC Coating material Thickness, μm Surface roughness Ra, μm Surface hardness Hv
  A SCM420 carburizing stainless steel   0.04   59 SCM420 carburizing is stainless   0.03   59   α-C  1.1   0.03   1850
  B SCM420 carburizing stainless steel   0.04   59 SCM420 carburizing stainless steel   0.03   59   DLC(α-C:H)  1.1   0.03   1850
  C SCM420 carburizing stainless steel   0.04   59 SCM420 carburizing stainless steel   0.03   59 Nothing  -   -   -
Note: HRC indicates Rockwell hardness (C Scale)
Table 2
Embodiment Comparative example
  1-1   1-2   1-3   1-4   1-5   1-6   1-7   1-8   1-9   1-10   1-11   1-1   1-2
Sliding part   A   A   A   A   A   A   A   B   B   B   B   B   C
Base oil (%)   79.3   79.3   79.3   79.3   80   78.5 (commercial product, CVTF)   79.3   79.3   79.3   79.3   80   79.3
Aliphatic ester (%)   0.7   -   -   -   -   15   0.7   -   -   -   -   0.7
Aliphatic amine (%)   -   0.7   -   -   -   -   -   0.7   -   -   -   -
Amide (%)   -   -   0.7   -   -   -   -   -   0.7   -   -   -
Alcohol (%)   -   -   -   0.7   -   -   -   -   -   0.7   -   -
CVTF packs additive (%)   10   10   10   10   10   10   10   10   10   10   10   10
Polymethacrylates (%)   10   10   10   10   10   10   10   10   10   10   10   10
Coefficient of friction   0.035   0.04   0.04   0.04   0.07   0.03   0.035   0.09   0.1   0.1   0.1   0.13   0.12
Table 3
Sliding part type Ring Block
Basis material (matrix) Surface roughness Ra, μm Surface hardness HRC Basis material (matrix) Surface roughness Ra, μm Surface hardness HRC Coating material Thickness, μm Surface roughness Ra, μm Surface hardness Hv
A1 SCM420 carburizing rust steel   0.04 59 SCM420 carburizing stainless steel   0.03 59   α-C  1.1   0.03   1850
B1 SCM420 carburizing stainless steel   0.04 59 SCM420 carburizing stainless steel   0.03 59   DLC(α-C:H)  1.1   0.03   1850
C1 SCM420 carburizing stainless steel   0.04 59 SCM420 carburizing stainless steel   0.03 59 Nothing  -   -   -
Note: HRC indicates Rockwell hardness (C-Scale)
Table 4
Embodiment Comparative example
  2-1   2-2   2-3   2-4   2-5   2-6   2-7   2-8   2-9   2-10   2-11   2-12   2-1
Sliding part   A1   A1   A1   A1   A1   A1   A1   B1   B1   B1   B1   B1   C1
Base oil (%)   79.3   79.3   79.3   79.3   80   78.5 (commercial product, ATF)   79.3   79.3   79.3   79.3   80   79.3
Aliphatic ester (%)   0.7   -   -   -   -   15   0.7   -   -   -   -   0.7
Aliphatic amine (%)   -   0.7   -   -   -   -   -   0.7   -   -   -   -
Amide (%)   -   -   0.7   -   -   -   -   -   0.7   -   -   -
Alcohol (%)   -   -   -   0.7   -   -   -   -   -   0.7   -   -
CVTF packs additive (%)   10   10   10   10   10   10   10   10   10   10   10   10
Polymethacrylates (%)   10   10   10   10   10   10   10   10   10   10   10   10
Coefficient of friction   0.035   0.04   0.04   0.035   0.04   0.03   0.035   0.07   0.08   0.08   0.08   0.11   0.1

Claims (19)

1. the low friction sliding part in a kind of speed changer, which is at least one of the sliding part being in slidable contact with each other in the presence of transmission oil composition, which includes:
Basis material with sliding area；With
Hard carbon thin film on sliding surface coated in basis material sliding area, the hard carbon thin film contain the hydrogen no more than 20 atom %,
Wherein, transmission oil composition includes at least one of organic oxygen-containing compound and aliphatic amine compound.
2. low friction sliding part as described in claim 1, wherein speed changer is a kind of continuously variable transmission, and transmission oil composition is a kind of continuously variable transmission fluid composition.
3. low friction sliding part as claimed in claim 2, wherein hard carbon thin film contains the hydrogen no more than 10 atom %.
4. low friction sliding part as claimed in claim 2, wherein hard carbon thin film contains the hydrogen no more than 0.5 atom %.
5. low friction sliding part as claimed in claim 2, wherein before basis material is coated by hard carbon thin film, the sliding area of basis material has the surface roughness (Ra) no more than 0.1 μ.
6. low friction sliding part as claimed in claim 2, wherein hard carbon thin film has the thickness of surface hardness (Hv) and range between 0.3~2.0 μm with the micro Vickers range that measures under 10g load between 1000~3500.
7. low friction sliding part as claimed in claim 2, wherein organic oxygen-containing compound is to be included selected from least one of the group being made of the derivative of at least one monohydric alcohol, at least one polyalcohol, at least one carboxylic acid, at least one ether, the derivative of at least one monohydric alcohol, the derivative of at least one polyalcohol, the derivative of at least one carboxylic acid, the derivative of at least one ether and at least one ester compound, the organic oxygen-containing compound with 0.05~3.0% amount based on continuously variable transmission fluid composition total amount.
8. low friction sliding part as claimed in claim 2, wherein continuously variable transmission fluid composition contains the aliphatic amine compound of the hydrocarbon chain including 6~30 carbon atoms, and gross mass of the content based on continuously variable transmission fluid composition is 0.05~3.0 mass %.
9. low friction sliding part as claimed in claim 2, wherein continuously variable transmission fluid composition includes at least one of polybutenyl succinic acid imide and polybutenyl succinic imide derivative.
10. low friction sliding part as claimed in claim 9, wherein, at least one of polybutenyl succinic acid imide and polybutenyl succinic imide derivative are included with the amount based on 0.1~15 mass % of continuously variable transmission fluid composition gross mass.
11. low friction sliding part as described in claim 1, wherein speed changer is a kind of automatic transmission, and transmission oil composition is a kind of automatic transmission fluid composition.
12. low friction sliding part as claimed in claim 11, wherein hard carbon thin film contains the hydrogen no more than 10 atom %.
13. low friction sliding part as claimed in claim 11, wherein hard carbon thin film contains the hydrogen no more than 0.5 atom %.
14. low friction sliding part as claimed in claim 11, wherein before basis material is coated by hard carbon thin film, the sliding area of basis material has the surface roughness (Ra) no more than 0.1 μ.
15. low friction sliding part as claimed in claim 11, wherein hard carbon thin film has the thickness of surface hardness (Hv) and range between 0.3~2.0 μm with the micro Vickers range that measures under 10g load between 1000~3500.
16. low friction sliding part as claimed in claim 11, wherein organic oxygen-containing compound is at least one compound selected from the group being made of the derivative of at least one monohydric alcohol, at least one polyalcohol, at least one carboxylic acid, at least one ether, the derivative of at least one monohydric alcohol, the derivative of at least one polyalcohol, the derivative of at least one carboxylic acid, the derivative of at least one ether and at least one ester, which is included with the amount based on automatic transmission fluid total composition 0.05~3.0%.
17. low friction sliding part as claimed in claim 11, wherein continuously variable transmission fluid composition contains the aliphatic amine compound of the hydrocarbon chain including 6~30 carbon atoms, and gross mass of the content based on automatic transmission fluid composition is 0.05~3.0 mass %.
18. low friction sliding part as claimed in claim 11, wherein automatic transmission fluid composition includes at least one of polybutenyl succinic acid imide and polybutenyl succinic imide derivative.
19. low friction sliding part as claimed in claim 18, wherein at least one of the polybutenyl succinic acid imide and polybutenyl succinic imide derivative is included with the amount based on 0.1~15 mass % of automatic transmission fluid composition gross mass.
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JP2004230039A JP4973973B2 (en) 2003-08-22 2004-08-06 Low friction sliding member for automatic transmission and automatic transmission oil composition used therefor
JP2004230038A JP4973972B2 (en) 2003-08-22 2004-08-06 Low friction sliding member for continuously variable transmission and continuously variable transmission oil composition used therefor
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